一价金磷化物配合物：合成、结构与反应活性

Gold(I) phosphido complexes: synthesis, structure, and reactivity.

作者信息

Stefanescu Diana M, Yuen Holming F, Glueck David S, Golen James A, Zakharov Lev N, Incarvito Christopher D, Rheingold Arnold L

机构信息

6128 Burke Laboratory, Department of Chemistry and Dartmouth Molecular Materials Group, Dartmouth College, Hanover, New Hampshire 03755, USA.

出版信息

Inorg Chem. 2003 Dec 29;42(26):8891-901. doi: 10.1021/ic035006e.

DOI:10.1021/ic035006e

PMID:14686872

Abstract

Deprotonation of the phosphine complexes Au(PHR(2))Cl with aqueous ammonia gave the gold(I) phosphido complexes Au(PR(2))() (PR(2) = PMes(2) (1), PCy(2) (2), P(t-Bu)(2) (3), PIs(2) (4), PPhMes (5), PHMes (6); Mes = 2,4,6-Me(3)C(6)H(2), Is = 2,4,6-(i-Pr)(3)C(6)H(2), Mes = 2,4,6-(t-Bu)(3)C(6)H(2), Cy = cyclo-C(6)H(11)). (31)P NMR spectroscopy showed that these complexes exist in solution as mixtures, presumably oligomeric rings of different sizes. X-ray crystallographic structure determinations on single oligomers of 1-4 revealed rings of varying size (n = 4, 6, 6, and 3, respectively) and conformation. Reactions of 1-3 and 5 with PPN[AuCl(2)] gave PPN[(AuCl)(2)(micro-PR(2))] (9-12, PPN = (PPh(3))(2)N(+)). Treatment of 3 with the reagents HI, I(2), ArSH, LiP(t-Bu)(2), and [PH(2)(t-Bu)(2)]BF(4) gave respectively Au(PH(t-Bu)(2))(I) (14), Au(PI(t-Bu)(2))(I) (15), Au(PH(t-Bu)(2))(SAr) (16, Ar = p-t-BuC(6)H(4)), Li[Au(P(t-Bu)(2))(2)] (17), and [Au(PH(t-Bu)(2))(2)]BF(4) (19).

摘要

膦配合物Au(PHR₂)Cl与氨水发生去质子化反应，生成了金(I)磷化物配合物[Au(PR₂)]ₙ（PR₂ = PMes₂ (1)、PCy₂ (2)、P(t-Bu)₂ (3)、PIs₂ (4)、PPhMes (5)、PHMes (6)；Mes = 2,4,6-Me₃C₆H₂，Is = 2,4,6-(i-Pr)₃C₆H₂，Mes = 2,4,6-(t-Bu)₃C₆H₂，Cy = 环-C₆H₁₁）。³¹P核磁共振光谱表明，这些配合物在溶液中以混合物形式存在，推测是不同大小的低聚环。对1 - 4的单个低聚物进行X射线晶体结构测定，揭示了不同大小（分别为n = 4、6、6和3）和构象的环。1 - 3和5与PPN[AuCl₂]反应生成PPN[(AuCl)₂(μ-PR₂)]（9 - 12，PPN = (PPh₃)₂N⁺）。用试剂HI、I₂、ArSH、LiP(t-Bu)₂和[PH₂(t-Bu)₂]BF₄处理3，分别得到Au(PH(t-Bu)₂)(I) (14)、Au(PI(t-Bu)₂)(I) (15)、Au(PH(t-Bu)₂)(SAr) (16，Ar = p-t-BuC₆H₄)、Li[Au(P(t-Bu)₂)₂] (17)和[Au(PH(t-Bu)₂)₂]BF₄ (19)。